Lubricant composition

ABSTRACT

A lubricant composition includes a base oil present in an amount of greater than 70 parts by weight per 100 parts by weight of the lubricant composition and an antioxidant. The antioxidant has the structure: wherein each X is independently C-A or N, so long as at least one X is N but no more than two of X are N. Moreover, A is H, cyano or an electron donating group that: (1) has an atom having at least one lone pair of electrons that is bonded directly to the aromatic ring; or (2) is an aryl group or alkyl group. Further, each R is independently H, an alkyl group, or aryl group and each R′ is independently an alkyl group or an aryl group.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a continuation of U.S. patent application Ser. No.15/756,782 filed on Mar. 1, 2018, now U.S. Pat. No. 10,662,390 dated May26, 2020, which is a national phase entry of International ApplicationNo. PCT/US2016/050149, filed on Sep. 2, 2016, which claims the benefitof U.S. Provisional Patent Application No. 62/213,241, filed on Sep. 2,2015. The contents of these applications are hereby incorporated byreference in their entirety.

FIELD OF THE DISCLOSURE

This disclosure generally relates to a lubricant composition. Morespecifically, the lubricant composition includes a particularantioxidant that includes an electron donating group.

BACKGROUND

Lubricant compositions are generally well known in the art and arebroadly categorized as oil or water based compositions, i.e.,compositions that include large weight percentages of non-polarcompounds (such as (base) oils) or large weight percentages of water,respectively. Lubricant compositions are typically further categorizedas engine oils, driveline system oils, gear oils, greases, automatic andmanual transmission fluids and oils, hydraulic oils, industrial gearoils, turbine oils, rust and oxidation (R&O) inhibited oils, compressoroils, or paper machine oils, etc. Each of these compositions hasparticular specifications and design requirements and most are designedto minimize corrosion and wear, to resist thermal and physicalbreakdown, and to be able to minimize the effects of common contaminantssuch as oxidizing compounds and metal fragments.

Antioxidants are compounds that can retard oxidation, and thus areuseful as additives in such lubricant compositions. Antioxidants arecommonly utilized in lubricant compositions to assist in reducingunwanted oxidation and increasing performance standards. Combustionengine lubricants oxidize readily at the high operating temperatures ofan engine, and in turn, have diminished lubricating capacity as theviscosity of the lubricant increases. Oxidation products also tend toaccumulate to form deposits, which in turn leads to greater wear onengine parts. For example, peroxyl radicals can lead to formation ofradical chains and ultimately oxidative degradation. Antioxidants areused to react with such radicals, shorten radical chains, and reducedegradation. Unfortunately, many antioxidants do not react as fast aswould be desired. Therefore, remains an opportunity for development ofimproved antioxidants.

SUMMARY OF THE DISCLOSURE

This disclosure provides a lubricant composition that includes a baseoil present in an amount of greater than 70 parts by weight per 100parts by weight of the lubricant composition and also includes anantioxidant. The antioxidant has the structure:

wherein each X is independently C-A or N, so long as at least one X is Nbut no more than two of X are N. Moreover, A is H, cyano or an electrondonating group that: (1) has an atom having at least one lone pair ofelectrons that is bonded directly to the aromatic ring; or (2) is anaryl group or alkyl group. Further, each R is independently H, an alkylgroup, or aryl group and each R′ is independently an alkyl group or anaryl group.

DETAILED DESCRIPTION OF THE DISCLOSURE

The present disclosure provides a lubricant composition. In variousembodiments, the lubricant composition can be further described as afully formulated lubricant or alternatively as an engine oil, adriveline system oil, a gear oil, a grease, an automatic and/or manualtransmission fluid and/or oil, a hydraulic oil, an industrial gear oil,a turbine oil, a rust and oxidation (R&O) inhibited oil, a compressoroil, a paper machine oil, and/or combinations thereof.

In one embodiment, the terminology “fully formulated lubricant” refersto a total final composition that is a final commercial oil. This finalcommercial oil may include, for instance, detergents, dispersants,antioxidants, antifoam additives, pour point depressants, viscosityindex improvers, anti-wear additives, friction modifiers, and othercustomary additives, depending on the formulation application. In theart, engine oils may be referred to as including a base oil as describedbelow and performance additives. The lubricant composition of thisdisclosure includes a base oil and a particular antioxidant and mayinclude any one or more of the aforementioned additives.

Base Oil:

The base oil is not particularly limited and may be further defined asincluding one or more oils of lubricating viscosity such as natural andsynthetic lubricating or base oils and mixtures thereof. In oneembodiment, the base oil is further defined as a lubricant. In anotherembodiment, the base oil is further defined as an oil of lubricatingviscosity. In still another embodiment, the base oil is further definedas a crankcase lubricating oil for spark-ignited and compression ignitedinternal combustion engines, including automobile and truck engines,two-cycle engines, aviation piston engines, and marine and railroaddiesel engines. Alternatively, the base oil can be further defined as anoil to be used in gas engines, stationary power engines, and turbines.The base oil may be further defined as a heavy or light duty engine oil.In one embodiment, the base oil is further defined as a heavy dutydiesel engine oil. Alternatively, the base oil may be described as anoil of lubricating viscosity or lubricating oil, for instance asdisclosed in U.S. Pat. No. 6,787,663 and U.S. 2007/0197407, each ofwhich is expressly incorporated herein by reference in one or morenon-limiting embodiments. Alternatively, the base oil may be used in oras an engine oil, driveline system oil, gear oil, grease, automatic andmanual transmission fluid or oil, hydraulic oil, industrial gear oil,turbine oil, rust and oxidation (R&O) inhibited oil, compressor oil, orpaper machine oil, etc.

The base oil may be further defined as a base stock oil. Alternatively,the base oil may be further defined as a component that is produced by asingle manufacturer to the same specifications (independent of feedsource or manufacturer's location) that meets the same manufacturer'sspecification and that is identified by a unique formula, productidentification number, or both. The base oil may be manufactured orderived using a variety of different processes including but not limitedto distillation, solvent refining, hydrogen processing, oligomerization,esterification, and re-refining. Re-refined stock is typicallysubstantially free from materials introduced through manufacturing,contamination, or previous use. In one embodiment, the base oil isfurther defined as a base stock slate, as is known in the art.

Alternatively, the base oil may be derived from hydrocracking,hydrogenation, hydrofinishing, refined and re-refined oils or mixturesthereof or may include one or more such oils. In one embodiment, thebase oil is further defined as an oil of lubricating viscosity such as anatural or synthetic oil and/or combinations thereof. Natural oilsinclude, but are not limited to, animal oils and vegetable oils (e.g.,castor oil, lard oil) as well as liquid petroleum oils andsolvent-treated or acid-treated mineral lubricating oils such asparaffinic, naphthenic or mixed paraffinic-naphthenic oils.

In various other embodiments, the base oil may be further defined as anoil derived from coal or shale. Non-limiting examples of suitable oilsinclude hydrocarbon oils such as polymerized and interpolymerizedolefins (e.g., polybutylenes, polypropylenes, propylene-isobutylenecopolymers, poly(1-hexenes), poly(1-octenes), poly(1-decenes), andmixtures thereof: alkylbenzenes (e.g., dodecylbenzenes,tetradecylbenzenes, dinonylbenzenes, and di(2-ethylhexyl)-benzenes);polyphenyls (e.g., biphenyls, terphenyls, and alkylated polyphenyls),alkylated diphenyl ethers and alkylated diphenyl sulfides and thederivatives, analogs, and homologs thereof.

In still other embodiments, the base oil may be further defined as asynthetic oil which may include one or more alkylene oxide polymers andinterpolymers and derivatives thereof wherein terminal hydroxyl groupsare modified by esterification, etherification, or similar reactions.Typically, these synthetic oils are prepared through polymerization ofethylene oxide or propylene oxide to form polyoxyalkylene polymers whichcan be further reacted to form the oils. For example, alkyl and arylethers of these polyoxyalkylene polymers (e.g., methylpolyisopropyleneglycol ether having a weight average weight average molecular weight of1.000; diphenyl ether of polyethylene glycol having a weight averagemolecular weight of 500-1,000; and diethyl ether of polypropylene glycolhaving a weight average molecular weight of 1.000-1.500) and/or mono-and polycarboxylic esters thereof (e.g. acetic acid esters, mixed C₃-C₈fatty acid esters, or the C₁₃ oxo acid diester of tetraethylene glycol)may also be utilized.

In even further embodiments, the base oil may include esters ofdicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinicacids and alkenyl succinic acids, maleic acid, azelaic acid, subericacid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer,malonic acid, alkyl malonic acids, and alkenyl malonic acids) with avariety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, and propylene glycol). Specific examples of these estersinclude, but are not limited to, dibutyl adipate, di(2-ethylhexylsebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate,diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosylsebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complexester formed by reacting one mole of sebacic acid with two moles oftetraethylene glycol and two moles of 2-ethylhexanoic acid, andcombinations thereof. Esters useful as the base oil or as included inthe base oil also include those formed from C₅ to C₁₂ monocarboxylicacids and polyols and polyol ethers such as neopentyl glycol,trimethylolpropane, pentaerythritol, dipentaerythritol, andtripentaerythritol.

The base oil may be alternatively described as a refined and/orre-refined oil, or combinations thereof. Unrefined oils are typicallyobtained from a natural or synthetic source without further purificationtreatment. For example, a shale oil obtained directly from retortingoperations, a petroleum oil obtained directly from distillation, or anester oil obtained directly from an esterification process and usedwithout further treatment, could all be utilized in this disclosure.Refined oils are similar to the unrefined oils except that theytypically have undergone purification to improve one or more properties.Many such purification techniques are known to those of skill in the artsuch as solvent extraction, acid or base extraction, filtration,percolation, and similar purification techniques. Re-refined oils arealso known as reclaimed or reprocessed oils and often are additionallyprocessed by techniques directed to removal of spent additives and oilbreakdown products.

The base oil may alternatively be described as specified in the AmericanPetroleum Institute (API) Base Oil Interchangeability Guidelines. Inother words, the base oil may be further described as one or acombination of more than one of five base oil groups: Group I (sulfurcontent >0.03 wt %, and/or <90 wt % saturates, viscosity index 80-120);Group II (sulfur content less than or equal to 0.03 wt %, and greaterthan or equal to 90 wt % saturates, viscosity index 80-120); Group III(sulfur content less than or equal to 0.03 wt %, and greater than orequal to 90 wt % saturates, viscosity index greater than or equal to120); Group IV (all polyalphaolefins (PAO's)): and Group V (all othersnot included in Groups I, II, III, or IV). In one embodiment, the baseoil is chosen from API Group I, II, III, IV, V and combinations thereof.In another embodiment, the base oil is chosen from API Group II, III,IV, and combinations thereof. In still another embodiment, the base oilis further defined as an API Group II, III, or IV oil and includes amaximum of about 49.9 wt %, typically up to a maximum of about 40 wt %,more typically up to a maximum of about 30 wt %, even more typically upto a maximum of about 20 wt %, even more typically up to a maximum ofabout 10 wt % and even more typically up to a maximum of about 5 wt % ofthe lubricating oil an API Group I or V oil. It is also contemplatedthat Group II and Group II basestocks prepared by hydrotreatment,hydrofinishing, hydroisomerization or other hydrogenative upgradingprocesses may be included in the API Group II described above. Moreover,the base oil may include Fisher Tropsch or gas to liquid GTL oils. Theseare disclosed for example in U.S. 2008/0076687, which is expresslyincorporated herein by reference in one or more non-limitingembodiments.

The base oil is typically present in the composition in an amount offrom 70 to 99.9, from 80 to 99.9, from 90 to 99.9, from 75 to 95, from80 to 90, or from 85 to 95, parts by weight per 100 parts by weight ofthe composition. Alternatively, the base oil may be present in amountsof greater than 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or99, parts by weight per 100 parts by weight of the composition. Invarious embodiments, the amount of lubricating oil in a fully formulatedlubricant (including diluent or carrier oils presents) is from about 80to about 99.5 percent by weight, for example, from about 85 to about 96percent by weight, for instance from about 90 to about 95 percent byweight. Of course, the weight, percent of the base oil may be any valueor range of values, both whole and fractional, within those ranges andvalues described above and/or may vary from the values and/or range ofvalues above by ±5%, ±10%, ±15%, ±20%, ±25%, ±30%, etc.

Antioxidant:

The lubricant composition also includes an antioxidant. One or more ofsuch antioxidants can be used. The antioxidant has the structure:

wherein each X is independently C-A or N, i.e., a carbon atom bonded toan “A” group or a nitrogen atom (N), so long as at least one X is N.However, no more than two of X are N. Moreover, A is H (i.e., a hydrogenatom), a cyano group or an electron donating group that: (1) has an atomhaving at least one lone pair of electrons that is bonded directly tothe aromatic ring: or (2) is an aryl group or alkyl group. Further, eachR is independently H, an alkyl group, or aryl group and each R′ isindependently an alkyl group or an aryl group.

In other embodiments, the antioxidant has the structure:

wherein each X is independently CH or N, so long as at least one X is Nand wherein A is an electron donating group. The electron donating group(1) has an atom having at least one lone pair of electrons that isbonded directly to the aromatic ring or (2) is an aryl group or alkylgroup. Moreover, each R is independently an alkyl group or aryl groupwhich may be any known in the art.

The terminology “aryl” group describes any functional group orsubstituent derived from an aromatic ring, e.g. phenyl, naphthyl,thienyl, indolyl, etc. The alkyl group may be linear, branched, orcyclic and typically includes 1 to 20 carbon atoms. The alkyl group mayinclude more than 20 carbon atoms. In various embodiments, the alkylgroup includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, or 20 carbon atoms or any range thereof. The alkyl group maybe further defined as an alkane, an alkene, or an alkane. The alkylgroup may be alternatively described using the formula C_(n)H_(2n+1)wherein n is 1 to 20, as described above. In various embodiments, thealkyl group may be described as methyl, ethyl propyl, butyl, t-butyl,pentyl, hexyl, octyl, nonyl, or any isomer thereof.

In various embodiments, the antioxidant has the structure:

Examples of additional embodiments are as follows:

When one or more carbon atoms within the aromatic ring of theantioxidant is replaced with nitrogen, the resulting compounds may haveimproved estimated activation enthalpies (ΔH*) for reactions withperoxyl radicals, while also maintaining a relatively high estimatedionization enthalpy (ΔH<ioη>) which reflects their stability in air, ascompared to the same compounds without the substitution of the nitrogenfor carbon. Substitution of nitrogen atoms may produce an increase inthe ionization enthalpy (ΔH′_(oη)), thus stabilizing the compound toone-electron oxidation (such as by reaction with O₂ in air orhydroperoxides arising from hydrocarbon oxidation). This stability maypermit substitution with electron-donating groups to increasereactivities as radical-trapping antioxidants by lowering the activationenthalpy (ΔH*) for reactions with peroxyl radicals.

The electron donating group (1) has an atom having at least one lonepair of electrons that is bonded directly to the aromatic ring of theantioxidant or (2) is an aryl group or alkyl group. The electrondonating group can be alternatively described as an “EDG”, as isappreciated in the art. In various embodiments, the electron donatinggroup has an atom, such a nitrogen atom, a phosphorous atom, an oxygenatom or a sulfur atom, that has at least one lone pair of electrons. Forexample, oxygen and sulfur each typically have two lone pairs ofelectrons while nitrogen and phosphorous each typically have only onelone pair of electrons. The terminology “lone pair” describes a pair ofvalence electrons that are not shared with other atoms and/or are notused in chemical bonding. These electrons may also be described as anon-bonding pair of electrons. Lone pair electrons are found in theoutermost electron shell of atoms. The number of lone pair electronsplus the number of bonding electrons equals the total number of valenceelectrons around an atom. Examples of atoms having at least one lonepair of electrons that is bonded directly to the aromatic ring of theantioxidant are as follows:

The electron donating group can alternatively be an aryl group or alkylgroup. The terminology “aryl” group describes any functional group orsubstituent derived from an aromatic ring, e.g. phenyl, naphthyl,thienyl, indolyl, etc. The alkyl group may be linear, branched, orcyclic and typically includes 1 to 20 carbon atoms. Although, the alkylgroup may include more than 20 carbon atoms. In various embodiments, thealkyl group includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, or 20 carbon atoms or any range thereof. The alkyl groupmay be further defined as an alkane, an alkene, or an alkane. The alkylgroup may be alternatively described using the formula C_(n)H_(2n+1)wherein n is 1 to 20, as described above. In various embodiments, thealkyl group may be described as methyl, ethyl propyl, butyl, t-butyl,pentyl, hexyl, octyl, nonyl, or any isomer thereof.

In other embodiments, the electron donating group is —NR″₂, —NH₂, —OH,—OR″, —NHCOR″, or —OCOR″, wherein each R″ is independently an alkylgroup having 1 to 10 carbon atoms, as described above. For example, theelectron donating group may be —NR″₂, wherein each R″ is independentlyan alkyl group having 1 to 10 carbon atoms, as described above. Inanother embodiment, the electron donating group is —NH₂. In anotherembodiment, the electron donating group is —OH. In a further embodiment,the electron donating group is —OR″, wherein R″ is an alkyl group having1 to 10 carbon atoms, as described above. In a further embodiment, theelectron donating group is —NHCOR″, wherein R″ is an alkyl group having1 to 10 carbon atoms, as described above. In another embodiment, theelectron donating group is —OCOR″. wherein R″ is an alkyl group having 1to 10 carbon atoms, as described above. Non-limiting examples ofstructures corresponding to such embodiments are set forth below:

In various non-limiting embodiments, analogs of the each of theaforementioned structures wherein one, two, or three of the methylgroups are each independent R, as described above, are expresslycontemplated.

In other embodiments, the electron donating group may be described asaromatic or aliphatic. In still other embodiments, the electron donatinggroup includes or is a hydrocarbon group, an alkoxy group (OR³), anamine group, a monosubstituted amine group (NHR³), or a disubstitutedamine group (NR³ ₂). In other embodiments, the electron donating groupmay be a diallyl amine. The electron-donating strength of the alkoxy oramine group comes largely from the lone pairs of electrons on the O andN atoms, respectively, such that each of R³ groups can be a hydrogen ora saturated or unsaturated branched or straight chain hydrocarbon moietyand/or may include one or more cycloaliphatic groups and/or one or morearomatic hydrocarbons, or a combination thereof, while not detractingfrom the electron donating characteristic of the alkoxy or amine group.In such embodiments, the term “cycloaliphatic” describes a saturated orunsaturated carbocyclic moiety comprising mono- or bicyclic rings.Cycloaliphatic groups typically include a 3- to 7-membered saturatedcarbocyclic moiety. Examples of cycloaliphatic moieties include, but arenot limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclohepyl, and the like, including partially unsaturated derivativesthereof such as cyclohexenyl, cyclopentenyl, and the like.Alternatively, the term “hydrocarbon group” may describe a hydrocarbonincluding from 1 to 20 carbon atoms, e.g. as described above, andincludes saturated or unsaturated, branched or straight chainhydrocarbon moieties, including aliphatic moieties and/or one or morecycloaliphatic groups and/or one or more aromatic hydrocarbons, or acombination thereof.

The electron donating group may alternatively be a thiol, sulfide,thioether, or thioester (e.g. wherein the sulfur atom of the group isadjacent to the group being donated into). Alternatively, the electrondonating group may be a phosphane.

In still other embodiments, the antioxidant has the following structure:

In addition, combinations of any one or more of the aforementionedantioxidants may be utilized.

The antioxidant is typically present in an amount of, or less than, 30,25, 20, 15, 10, 5, 2, 1.5, 1, or 0.5, parts by weight per 100 parts byweight of the lubricant composition. In various embodiments, theantioxidant is present in an amount of from of from 0.1 to 2, 0.5 to 2,1 to 2, or 1.5 to 2, parts by weight per 100 parts by weight of thelubricant composition. Of course, the weight percent of the antioxidantmay be any value or range of values, both whole and fractional, withinthose ranges and values described above and/or may be present in amountsthat vary from the values and/or range of values above by ±5%, ±10%,±15%, ±20%, ±25%, ±30%, etc.

Additives:

The composition can additionally include one or more additives toimprove various chemical and/or physical properties. Non-limitingexamples of the one or more additives include anti-wear additives, metalpassivators, rust inhibitors, viscosity index improvers, pour pointdepressors, dispersants, detergents, and antifriction additives. One ormore of the additives may be ash-including or ash-less.

Anti-Wear Additive:

The anti-wear additive is not particularly limited and may be any knownin the art. In one embodiment, the anti-wear additive is selected fromthe group of ZDDP, zinc dialkyl-dithio phosphates, and combinationsthereof. Alternatively, the anti-wear additive may include sulfur-and/or phosphorus- and/or halogen-including compounds, e.g. sulfurisedolefins and vegetable oils, zinc dialkyldithiophosphates, alkylatedtriphenyl phosphates, tritolyl phosphate, tricresyl phosphate,chlorinated paraffins, alkyl and aryl di- and trisulfides, amine saltsof mono- and dialkyl phosphates, amine salts of methylphosphonic acid,diethanolaminomethyltolyltriazole,bis(2-ethylhexyl)aminomethyltolyltriazole, derivatives of2,5-dimercapto-1,3,4-thiadiazole, ethyl3-[(diisopropoxyphosphinothioyl)thiol propionate, triphenylthiophosphate (triphenylphosphorothioate), tris(alkylphenyl)phosphorothioate and mixtures thereof (for example tris(isononylphenyl)phosphorothioate), diphenyl monononylphenyl phosphorothioate,isobutylphenyl diphenyl phosphorothioate, the dodecylamine salt of3-hydroxy-1,3-thiaphosphetane 3-oxide, trithiophosphoric acid5,5,5-tris[isooctyl 2-acetate], derivatives of 2-mercaptobenzothiazolesuch asN,N-bis(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiazole,ethoxycarbonyl-5-octyldithiocarbamate, and/or combinations thereof. Inone embodiment, the anti-wear additive include phosphorous and sulfur,e.g. in phosphorothionates and/or dithiophosphate esters.

The anti-wear additive is typically present in the composition in anamount of from 0.1 to 20, from 0.5 to 15, from 1 to 10, from 5 to 10,from 5 to 15, from 5 to 20, from 0.1 to 1, from 0.1 to 0.5, or from 0.1to 1.5, parts by weight per 100 parts by weight of the composition.Alternatively, the anti-wear additive may be present in amounts of lessthan 20, less than 15, less than 10, less than 5, less than 1, less than0.5, or less than 0.1, parts by weight per 100 parts by weight of thecomposition. It is also contemplated that the antiwear additive may bepresent in an amount of from 0.2 to 0.8, from 0.2 to 0.6, from 0.2 to0.4, or from 0.3 to 0.5, parts by weight per 100 parts by weight of thecomposition. Of course, the weight percent of the anti-wear additive maybe any value or range of values, both whole and fractional, within thoseranges and values described above and/or may vary from the values and orrange of values above by ±5%, ±10%, ±15%, ±20%, ±25%, ±30%, etc.

Additional Antioxidants:

The lubricant composition may include one or more additionalantioxidants in addition to the antioxidant described above. Suitable,non-limiting, additional antioxidants include alkylated monophenols, forexample 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol2,4-dimethyl-6(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol, and combinations thereof.

Other non-limiting examples of suitable additional antioxidants includesalkylthiomethyl phenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-didodecylthiomethyl-4-nonylphenol, and combinations thereof.Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate, andcombinations thereof, may also be utilized.

Furthermore, hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide, and combinationsthereof, may also be used.

It is also contemplated that alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, andcombinations thereof may be utilized as additional antioxidants.

O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate, andcombinations thereof, may also be utilized.

Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,and combinations thereof are also suitable for use as additionalantioxidants.

Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, andcombinations thereof, may also be used.

Additional suitable, but non-limiting examples of additionalantioxidants include aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and combinationsthereof. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy 3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and combinationsthereof, may also be utilized. In addition, acylaminophenols, forexample 4-hydroxylauranilide, 4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate can be used.

Esters of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, andcombinations thereof, may also be used. It is further contemplated thatesters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene diethylene glycol, triethylene glycol,pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, andcombinations thereof, may be used. Esters of13-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- orpolyhydric alcohols, e.g. with methanol, ethanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, andcombinations thereof, may also be used. Moreover, esters of3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydricalcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol,1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,thiodiethylene glycol, diethylene glycol, triethylene glycol,pentaerythritol, tris(hydroxyethyl) isocyanurateN,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and combinationsthereof, may be utilized.

Additional non-limiting examples of suitable additional antioxidantsinclude those that include nitrogen, such as amides ofβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydropenylpropionyl)hydrazine. Othersuitable non-limiting examples of additional antioxidants include aminicantioxidants such as N,N′-diisopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylateddiphenylamine, for example p,p′-di-tert-octyldiphenylamine,4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol,4-dodecanoylaminophenol, 4-octadecanoylaminophenol,bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated isopropyl/isohexyldiphenylamines, mixtures of mono- anddialkylated tert-butyldiphenylamines,2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one and2,2,6,6-tetramethylpiperidin-4-ol, and combinations thereof.

Even further non-limiting examples of suitable additional antioxidantsincludes aliphatic or aromatic phosphites, esters of thiodipropionicacid or of thiodiacetic acid, or salts of dithiocarbamic ordithiophosphoric acid,2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,1trithiatridecane and2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane, andcombinations thereof. Furthermore, sulfurized fatty esters, sulfurizedfats and sulfurized olefins, and combinations thereof, may be used.

The one or more additional antioxidants are not particularly limited inamount in the composition but may be present such that a total amount ofantioxidants in the composition is about, or less than, 30, 25, 20, 15,10, 5, 2, 1.5, 1, or 0.5, of from 0.1 to 2, 0.5 to 2, 1 to 2, or 1.5 to2, parts by weight per 100 parts by weight of the composition.Alternatively, the total amount of antioxidants in the composition maybe less than 2, less than 1.5, less than 1, or less than 0.5, parts byweight per 100 parts by weight of the composition. Of course, the weightpercent of the one or more additional antioxidants may be any value orrange of values, both whole and fractional, within those ranges andvalues described above and/or may be present in amounts that vary fromthe values and or range of values above by ±5%, ±10%, ±15%, ±20%, ±25%,±30%, etc.

Metal Deactivators:

In various embodiments, one or more metal deactivators can be includedin the composition. Suitable, non-limiting examples of the one or moremetal deactivators include benzotriazoles and derivatives thereof, forexample 4- or 5-alkylbenzotriazoles (e.g. triazole) and derivativesthereof, 4,5,6,7-tetrahydrobenzotriazole and5,5′-methylenebisbenzotriazole; Mannich bases of benzotriazole ortriazole, e.g. 1-[bis(2-ethylhexyl)aminomethyl)triazole and1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; andalkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)benzotriazole,1-(1-butoxyethyl)benzotriazole and 1-(1-cyclohexyloxybutyl)triazole, andcombinations thereof.

Additional non-limiting examples of the one or more metal deactivatorsinclude 1,2,4-triazoles and derivatives thereof, for example 3-alkyl(oraryl)-1,2,4-triazoles, and Mannich bases of 1,2,4-triazoles, such as1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole;alkoxyalkyl-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole;and acylated 3-amino-1,2,4-triazoles, imidazole derivatives, for example4,4′-methylenebis(2-undecyl-5-methylimidazole) andbis[(N-methyl)imidazol-2-yl]carbinol octyl ether, and combinationsthereof.

Further non-limiting examples of the one or more metal deactivatorsinclude sulfur-including heterocyclic compounds, for example2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole andderivatives thereof; and3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one, andcombinations thereof. Even further non-limiting examples of the one ormore metal deactivators include amino compounds, for examplesalicylidenepropylenediamine, salicylaminoguanidine and salts thereof,and combinations thereof.

The one or more metal deactivators are not particularly limited inamount in the composition but are typically present in an amount of from0.01 to 0.1, from 0.05 to 0.01, or from 0.07 to 0.1, parts by weight per100 parts by weight of the composition. Alternatively, the one or moremetal deactivators may be present in amounts of less than 0.1, of lessthan 0.7, or less than 0.5, parts by weight per 100 parts by weight ofthe composition. The weight percent of the one or more metaldeactivators may be any value or range of values, both whole andfractional, within those ranges and values described above and/or may bepresent in amounts that vary from the values and/or range of valuesabove by ±5%, ±10%, ±15%, ±20%, ±25%, ±30%, etc.

Rust Inhibitors and Friction Modifiers:

In various embodiments, one or more additional rust inhibitors and/orone or more friction modifiers can be included in the composition.Suitable, non-limiting examples of the one or more additional rustinhibitors and/or one or more friction modifiers include organic acids,their esters, metal salts, amine salts and anhydrides, for examplealkyl- and alkenylsuccinic acids and their partial esters with alcohols,diols or hydroxycarboxylic acids, partial amides of alkyl- andalkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- andalkoxyethoxycarboxylic acids such as dodecyloxyacetic acid,dodecyloxy(ethoxy)acetic acid and the amine salts thereof, and alsoN-oleoylsarcosine, sorbitan monooleate, lead naphthenate,alkenylsuccinic anhydrides, for example dodecenylsuccinic anhydride,2-carboxymethyl-1-dodecyl-3-methylglycerol and the amine salts thereof,and combinations thereof. Additional suitable, non-limiting examples ofthe one or more rust inhibitors and/or friction modifiers includenitrogen-including compounds, for example, primary, secondary ortertiary aliphatic or cycloaliphatic amines and amine salts of organicand inorganic acids, for example oil-soluble alkylammonium carboxylates,and also 1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol,and combinations thereof. Further suitable, non-limiting examplesinclude heterocyclic compounds, for example: substituted imidazolinesand oxazolines, and 2-heptadecenyl-1-(2-hydroxyethyl)imidazoline,phosphorus-including compounds, for example: Amine salts of phosphoricacid partial esters or phosphonic acid partial esters, and zincdialkyldithiophosphates, molybdenum-including compounds, such asmolybdenum dithiocarbamate and other sulfur and phosphorus includingderivatives, sulfur-including compounds, for example: bariumdinonylnaphthalenesulfonates, calcium petroleum sulfonates,alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic2-sulfocarboxylic acids and salts thereof, glycerol derivatives, forexample: glycerol monooleate,1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols,1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols and2-carboxyalkyl-1,3-dialkylglycerols, and combinations thereof.

The one or more additional rust inhibitors and/or one or more frictionmodifiers are not particularly limited in amount in the composition butmay be present in an amount of from 0.05 to 0.5, 0.01 to 0.2, from 0.05to 0.2, 0.1 to 0.2, 0.15 to 0.2, or 0.02 to 0.2, parts by weight per 100parts by weight of the composition. Alternatively, the one or moreadditional rust inhibitors and/or one or more friction modifiers may bepresent in amounts of less than 0.5, less than 0.4, less than 0.3, lessthan 0.2, less than 0.1, less than 0.5, or less than 0.1, parts byweight per 100 parts by weight of the composition. The weight percent ofthe one or more rust inhibitors and friction modifiers may be any valueor range of values, both whole and fractional, within those ranges andvalues described above and/or may be present in amounts that vary fromthe values and/or range of values above by ±5%, ±10%, ±15%, ±20%, ±25%,±30%, etc.

Viscosity Index Improvers:

In various embodiments, one or more viscosity index improvers can beincluded in the composition. Suitable, non-limiting examples of the oneor more viscosity index improvers include polyacrylates,polymethacrylates, vinylpyrrolidone/methacrylate copolymers,polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene/acrylatecopolymers and polyethers, and combinations thereof. The one or moreviscosity index improvers are not particularly limited in amount in thecomposition but are typically present in an amount of from 1 to 1, from2 to 8, from 3 to 7, from 4 to 6, or from 4 to 5, parts by weight per100 parts by weight of the composition. Alternatively, the one or moreviscosity index improvers may be present in an amount of less than 10,9, 8, 7, 6, 5, 4, 3, 2, or 1, part by weight per 100 parts b eight ofthe composition. The weight percent of the one or more viscosity indeximprovers may be any value or range of values, both whole andfractional, within those ranges and values described above and/or may bepresent in amounts that vary from the values and/or range of valuesabove by ±5%, ±10%, ±15%, ±20%, ±25%, ±30%, etc.

Pour Point Depressants:

In various embodiments, one or more pour point depressants can beincluded in the composition. Suitable, non-limiting examples of the pourpoint depressants include polymethacrylate and alkylated naphthalenederivatives, and combinations thereof. The one or more pour pointdepressants are not particularly limited in amount in the compositionbut are typically present in an amount of from 0.1 to 1, from 0.5 to 1,or from 0.7 to 1, part by weight per 100 parts by weight of thecomposition. Alternatively, the one or more pour point depressants maybe present in amounts of less than 1, less than 0.7, or less than 0.5,parts by weight per 100 parts by weight of the composition. The weightpercent of the one or more pour point depressants may be any value orrange of values, both whole and fractional, within those ranges andvalues described above and/or may be present in amounts that vary fromthe values and/or range of values above by ±5%, ±10%, ±15%, ±20%, ±25%,±30%, etc.

Dispersants:

In various embodiments, one or more dispersants can be included in thecomposition. Suitable, non-limiting examples of the one or moredispersants include polybutenylsuccinic amides or -imides,polybutenylphosphonic acid derivatives and basic magnesium, calcium andbarium sulfonates and phenolates, succinate esters and alkylphenolamines (Mannich bases), and combinations thereof.

The one or more dispersants are not particularly limited in amount inthe composition but are typically present in an amount of from 0.1 to 5,from 0.5 to 4.5, from 1 to 4, from 1.5 to 3.5, from 2 to 3, or from 2.5to 3, parts by weight per 100 parts by weight of the composition.Alternatively, the one or more dispersants may be present in an amountof less than 5, 4.5, 3.5, 3, 2.5, 2, 1.5, or 1, part by weight per 100parts by weight of the composition. The weight percent of the one ormore dispersants may be any value or range of values, both whole andfractional, within those ranges and values described above and/or may bepresent in amounts that vary from the values and/or range of valuesabove by ±5%, ±10%, ±15%, ±20%, ±25%, ±30%, etc.

Detergents:

In various embodiments, one or more detergents can be included in thecomposition. Suitable, non-limiting examples of the one or moredetergents include overbased or neutral metal sulphonates, phenates andsalicylates, and combinations thereof.

The one or more detergents are not particularly limited in amount in thecomposition but are typically present in an amount of from 0.1 to 5,from 0.5 to 4.5, from 1 to 4, from 1.5 to 3.5, from 2 to 3, or from 2.5to 3, parts by weight per 100 parts by weight of the composition.Alternatively, the one or more detergents may be present in an amount ofless than 5, 4.5, 3.5, 3, 2.5, 2, 1.5, or 1, part by weight per 100parts by weight of the composition. The weight percent of the one ormore detergents may be any value or range of values, both whole andfractional, within those ranges and values described above and/or may bepresent in amounts that vary from the values and/or range of valuesabove by ±5%, ±10%, ±15%, ±20%, ±25%, ±30%, etc.

In various embodiments, the composition is substantially free of water,e.g. includes less than 5, 4, 3, 2, or 1, weight percent of water.Alternatively, the composition may include less than 0.5 or 0.1 weightpercent of water, less than 500, 100, 50, 20, 15, 10, or 5, parts byweight of water per one million parts by weight (ppm) of thecomposition, or may be free of water. Of course, the weight percent ofthe water may be any value or range of values, both whole andfractional, within those ranges and values described above and/or may bepresent in amounts that vary from the values and/or range of valuesabove by ±5%, ±10%, ±15%, ±20%, ±25%, ±30%, etc.

The lubricant composition may be further defined as ash-including orash-less, according to ASTM D 874 and known in the art. Typically, theterminology “ash-less” refers to the absence of (significant) amounts ofmetals such as sodium, potassium, calcium, and the like. Of course, itis to be understood that the lubricant composition is not particularlylimited to being defined as either ash-including or ash-less.

Additive Concentrate Package:

The instant disclosure also provides an additive concentrate packagewhich includes the antioxidant of this disclosure and also includes oneor more metal deactivators, one or more anti-wear additives, one or moreadditional antioxidants, and/or one or more of the aforementionedadditives. The additive concentrate package may include the antioxidantof this disclosure and be free of any additional antioxidants. In oneembodiment, the additive concentrate package is further defined as ahydraulic additive concentrate package. In another embodiment, theadditive concentrate package is further defined as an engine oiladditive concentrate package. In a further embodiment, the additiveconcentrate package is further defined as a driveline system oiladditive concentrate package. In an additional embodiment, the additiveconcentrate package is further defined as a gear oil additiveconcentrate package. In still another embodiment, the additiveconcentrate package is further defined as a grease additive concentratepackage. In a further embodiment, the additive concentrate package isfurther defined as an automatic and/or manual transmission fluid and/oroil additive concentrate package. In another embodiment, the additiveconcentrate package is further defined as an industrial gear oiladditive concentrate package. In another embodiment, the additiveconcentrate package is further defined as a turbine oil additiveconcentrate package. In another embodiment, the additive concentratepackage is further defined as a rust and oxidation inhibited oiladditive concentrate package. In another embodiment, the additiveconcentrate package is further defined as a compressor oil additiveconcentrate package. In another embodiment, the additive concentratepackage is further defined as a paper machine oil additive concentratepackage. In another embodiment, the additive concentrate package isfurther defined as an additive concentrate package for combinations oftwo or more of the aforementioned oils.

In another embodiment, the additive concentrate package includes 10-40weight percent of the antioxidant, 0-15 weight percent of a metaldeactivator (e.g. a yellow metal corrosion inhibitor), 0-15 weightpercent of a corrosion inhibitor (e.g. the corrosion inhibitor of thisdisclosure and a ferrous metal corrosion inhibitor), 0-10 weight percentof a friction modifier (e.g. glycerol mono-oleate), 20-35 weight percentof an anti-wear additive, and 0-1 weight percent of an anti-foamadditive. Additionally, 0-25 weight percent of a dispersant may also beincluded. Viscosity modifiers and pour point depressants may also beincluded but typically are not part of such packages.

Some of the compounds described above may interact in the lubricantcomposition, so the components of the lubricant composition in finalform may be different from those components that are initially added orcombined together. Some products formed thereby, including productsformed upon employing the composition of this disclosure in its intendeduse, are not easily described or describable. Nevertheless, all suchmodifications, reaction products, and products formed upon employing thecomposition of this disclosure in its intended use, are expresslycontemplated and hereby included herein in various non-limitingembodiments. Various embodiments of this disclosure include one or moreof the modification, reaction products, and products formed fromemploying the composition, as described above.

Method of Forming the Composition:

This disclosure also provides a method of forming the composition. Themethod includes the steps of providing the base oil, providing theantioxidant of this disclosure and combining the base oil and theantioxidant. The method may also include one or more steps of providingany one or more of the aforementioned additives and combining the one ormore aforementioned additives with the base oil and/or antioxidant ofthis disclosure in any order and in any amounts.

Antioxidant Independent from Composition:

This disclosure also provides the antioxidant itself independent fromany lubricant composition. The antioxidant may be any as describedherein.

Method of Making the Antioxidant:

This disclosure also provides a method of making the antioxidant. Invarious embodiments, the method includes the steps of providing an aminodialkylaminopyrimidine wherein the alkyl groups each independently havefrom 1 to 20 carbon atoms, providing a catalytic amount of iodine,providing acetone, and combining the amino dialkylaminopyrimidine, theiodine, and the acetone to form the antioxidant of this disclosure.

In other embodiments, the method may include one or more steps asoutline below. One of skill in the art may change the starting materialsas needed. For example, any suitable second amine may be utilized inplace of the bis-2-ethylhexylamine. In still other embodiments, themethod includes one or more steps as described in EP 94245, which isexpressly incorporated herein in its entirety in various non-limitingembodiments. For example, one of skill in the art may select one or moresynthetic steps from EP 94245 to form the antioxidant of the instantdisclosure.

The alkyl groups of the dialkylaminopyrimidine may each independently belinear, branched, or cyclic and typically includes 1 to 20 carbon atoms.The alkyl group may include more than 20 carbon atoms. In variousembodiments, the alkyl group includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms or any range thereof.The alkyl group may be further defined as an alkane, an alkene, or analkyne. The alkyl group may be alternatively described using the formulaC_(n)H_(2n+1) wherein n is 1 to 20, as described above. In variousembodiments, the alkyl group may be described as methyl, ethyl propyl,butyl, t-butyl, pentyl, hexyl, octyl, nonyl, or any isomer thereof.

In various non-limiting embodiments, one or more of the antioxidants ofthe instant disclosure may be utilized in combination with one or moreantioxidants described in provisional application Ser. No. 62/213,245,provisional application Ser. No. 62/213,241, provisional applicationSer. No. 62/213,239, provisional application Ser. No. 62/347,907, U.S.national stage application Ser. No. 15/756,782, which is a nationalstage entry of PCT application number PCT/US16/050149, and/or U.S.national stage application Ser. No. 15/756,848, which is a nationalstage entry of PCT application number PCT/US16/050140, each of whichU.S. application is expressly incorporated herein by reference in itsentirety in various non-limiting embodiments.

EXAMPLES

An example of the antioxidant of this disclosure can be formed asfollows:

Example 1

In a dry flask 5-amino-N,N-dioctylaminopyrimidine and a catalytic amountof iodine are mixed with acetone as a solvent. The resultant reactionmixture is heated until complete. Upon completion of the reaction, themixture is cooled and the product is isolated.

Example 2

1,2-dihydro-6-methoxy-2,2,4-trimethyl-1,5-naphthyridine: In a 1 L 3 neckround bottom flask equipped with a reflux condenser connected to anitrogen gas source, a thermocouple, and a magnetic stir bar wasdissolved 52.48 g of 5-amino-2-methoxypyridine in 500 mL of acetone. Tothe resultant solution was added 6.8 g of iodine. The resultant mixturewas stirred under a nitrogen atmosphere and heated at reflux, internalmeasured reaction temperature was 60° C. After 14 hr of heating theresultant mixture was cooled to ambient temperature and concentratedunder vacuum to give a dark viscous crude oil. The crude reactionmixture was dissolved into dichloromethane and passed through a shortcolumn of silica gel eluting with dichloromethane to afford 69 g (80%yield) of 1,2-dihydro-6-methoxy-2,2,4-trimethyl-1,5-naphthyridine as ayellow oil. ¹H NMR (500 MHz, CDCl₃): δ 1.26 (s, 6H), 2.05 (s, 3H), 3.4(s, 1H), 3.86 (s, 3H), 5.49 (s, 1H), 6.4 (d, 1H), 6.7 (d, 1H). Thisreaction is also set forth visually below:

Example 3

6-methoxy-1,2,3,4-tetrahydro-2,2,4-trimethyl-1,5-naphthyridine: In a 600mL pressure bottle equipped with a magnetic stir bar was dissolved 10 gof 1,2-dihydro-6-methoxy-2,2,4-trimethyl-1,5-naphthyridine in 30 mL ofethanol. To the resultant solution was added 0.75 g of 10% Pd on carbonas a catalyst using an additional 25 mL of ethanol to ensure completetransfer of the catalyst to the flask. The resultant mixture was purgedwith nitrogen and was reacted under a hydrogen pressure of 20 to 40 psiuntil no further hydrogen was absorbed. The reaction mixture was purgedwith nitrogen and the catalyst removed by filtration. The filtrate wasconcentrated under vacuum to afford 9.93 g (98% yield) of6-methoxy-1,2,3,4-tetrahydro-2,2,4-trimethyl-1,5-naphthyridine as alight amber oil. ¹H NMR (500 MHz, CDCl₃): δ 1.17 (s, 3H), 1.24 (s, 3H),1.39 (d, 3H), 1.5 (t, 1H), 1.84 (dd, 1H), 2.93 (m, 1H), 3.05 (s, 1H),3.87 (s, 3H), 6.41 (d, 1H), 6.76 (d, 1H), MS: m/z=207 (M)′. Thisreaction is also set forth visually below:

After formation, the antioxidant formed in Example 3 is added to an oilwhich is evaluated to determine Oxidation Induction Time using HighPressure Differential Scanning calorimetry and ASTM D6186. Variouscomparative compositions are also formed that include none of theantioxidant. The results are set forth immediately below.

Oxidation Induction Time − mins Composition 1 16 0.5 wt % Antioxidant ofExample 3; HDDEO-Group III* Composition 2 20 1.5 wt % Antioxidant ofExample 3; HDDEO-Group III* Composition 3 27 2 wt % Antioxidant ofExample 3; HDDEO-Group II* Composition 4 8 2 wt % Antioxidant of Example3; EHC 45** Comparative Compositions 1 and 2 7 HDDEO-Group III; NoAntioxidant* Comparative Composition 3 4 HDDEO-Group II; No Antioxidant*Comparative Composition 4 3 EHC 45; No Antioxidant** *Run at 200° C.;500 psi; **Run at 200° C.; 150 psi

Based on the data shown in the Table above, use of the antioxidantsshows improved Oxidation Induction Time for compositions including 0.5-2wt % antioxidant compared to the Comparative Compositions withoutantioxidant present.

All combinations of the aforementioned embodiments throughout the entiredisclosure are hereby expressly contemplated in one or more non-limitingembodiments even if such a disclosure is not described verbatim in asingle paragraph or section above. In other words, an expresslycontemplated embodiment may include any one or more elements describedabove selected and combined from any portion of the disclosure.

One or more of the values described above may vary by ±5%, ±10%, ±15%,±20%, ±25%, etc. so long as the variance remains within the scope of thedisclosure. Unexpected results may be obtained from each member of aMarkush group independent from all other members. Each member may berelied upon individually and or in combination and provides adequatesupport for specific embodiments within the scope of the appendedclaims. The subject matter of all combinations of independent anddependent claims, both singly and multiply dependent, is hereinexpressly contemplated. The disclosure is illustrative including wordsof description rather than of limitation. Many modifications andvariations of the present disclosure are possible in light of the aboveteachings, and the disclosure may be practiced otherwise than asspecifically described herein.

It is also to be understood that any ranges and subranges relied upon indescribing various embodiments of the present disclosure independentlyand collectively fall within the scope of the appended claims, and areunderstood to describe and contemplate all ranges including whole and/orfractional values therein, even if such values are not expressly writtenherein. One of skill in the art readily recognizes that the enumeratedranges and subranges sufficiently describe and enable variousembodiments of the present disclosure, and such ranges and subranges maybe further delineated into relevant halves, thirds, quarters, fifths,and so on. As just one example, a range “of from 0.1 to 0.9” may befurther delineated into a lower third, i.e. from 0.1 to 0.3, a middlethird, i.e. from 0.4 to 0.6, and an upper third, i.e. from 0.7 to 0.9,which individually and collectively are within the scope of the appendedclaims, and may be relied upon individually and/or collectively andprovide adequate support for specific embodiments within the scope ofthe appended claims. In addition, with respect to the language whichdefines or modifies a range, such as “at least,” “greater than,” “lessthan,” “no more than,” and the like, it is to be understood that suchlanguage includes subranges and/or an upper or lower limit. As anotherexample, a range of “at least 10” inherently includes a subrange of fromat least 10 to 35, a subrange of from at least 10 to 25, a subrange offrom 25 to 35, and so on, and each subrange may be relied uponindividually and/or collectively and provides adequate support forspecific embodiments within the scope of the appended claims. Finally,an individual number within a disclosed range may be relied upon andprovides adequate support for specific embodiments within the scope ofthe appended claims. For example, a range “of from 1 to 9” includesvarious individual integers, such as 3, as well as individual numbersincluding a decimal point (or fraction), such as 4.1, which may berelied upon and provide adequate support for specific embodiments withinthe scope of the appended claims.

What is claimed is:
 1. A method of forming a lubricant composition,comprising: combining a base oil and an antioxidant to form thelubricant composition, wherein the antioxidant comprises the structure:

wherein each X is independently C-A or N, so long as at least one X is Nbut no more than two of X are N; and wherein A is H, cyano or anelectron donating group that: (1) has an atom having at least one lonepair of electrons that is bonded directly to the aromatic ring; or (2)is an aryl group or alkyl group; and wherein each R is independently H,an alkyl group, or aryl group and each R′ is independently an alkylgroup or an aryl group, with the proviso that in structure (A) when theX in the 8 position is N, at least one of the following substitutions ispresent: (i) at least one A is not H, (ii) another X is N, or (iii) theR attached to the carbon in the 2 position is not H.
 2. The method ofclaim 1, further comprising: forming the antioxidant, comprising:combining an amino dialkylaminopyrimidine, a catalytic amount of iodineand acetone to form the antioxidant, wherein the alkyl groups of thedialkylaminopyrimidine each independently comprise from 1 to 20 carbonatoms.
 3. The method of claim 2, wherein the alkyl groups of thedialkylaminopyrimidine is each independently linear, branched or cyclic.4. The method of claim 2, wherein the alkyl groups of thedialkylaminopyrimidine is each independently an alkane, an alkene or analkyne.
 5. The method of claim 2, wherein the alkyl groups of thedialkylaminopyrimidine is each independently a methyl, ethyl, propyl,butyl, t-butyl, pentyl, hexyl, octyl, nonyl or an isomer thereof.
 6. Themethod of claim 2, wherein the alkyl groups of thedialkylaminopyrimidine each independently comprises the formulaC_(n)H_(2n+1), wherein n is an integer from 1 to
 20. 7. The method ofclaim 1, wherein the base oil is present in an amount of greater than 70parts by weight per 100 parts by weight of the lubricant composition. 8.The method of claim 1, wherein the base oil comprises at least one of anAPI Group I, Group II and Group III oil.
 9. The method of claim 1,wherein the base oil comprises at least one of a mineral oil and asynthetic base oil.
 10. The method of claim 1, wherein said antioxidantcomprises the structure:


11. The method of claim 1, wherein said antioxidant comprises thestructure:


12. The method of claim 1, wherein A is an electron donating group thathas an oxygen atom or nitrogen atom that is bonded directly to thearomatic ring.
 13. The method of claim 1, wherein said electron donatinggroup is NR″₂, —NH₂, —OH, —OR″, —NHCOR″, or OCOR″, wherein each R″ isindependently an alkyl group having 1 to 10 carbon atoms.
 14. The methodof claim 1, wherein said electron donating group is NR″₂, —OR″, —NHCOR″or —OCOR″, wherein each R″ is an alkyl group having 1 to 10 carbonatoms.
 15. The method of claim 1, wherein said electron donating groupis an alkyl group having 1 to 20 carbon atoms.
 16. The method of claim1, wherein said electron donating group is an aryl group.
 17. The methodof claim 1, wherein two of X are N.
 18. The method of claim 1, whereinsaid antioxidant is present in an amount of from 0.1 to 2 parts byweight per 100 parts by weight of said lubricant composition.
 19. Themethod of claim 1, further comprising combining the base oil and theantioxidant with one or more additive.
 20. The method of claim 19,wherein the one or more additive comprises at least one of a detergent,a dispersant, an antifoam agent, an additional antioxidant, a pour pointdepressant, a viscosity index improver, an anti-wear agent and afriction modifier.